Method of treating hydrocarbon oils



Aug. 10, 1937. A. J. PARlS. JR 2,089,760

METHOD OF TREATING HYDROCARBON OILS Filed Oct. 25, 1954 HER? @(CHHNGE /M" yam; rr

mum-M 5 Patented Aug. 10, 1937 are!) STATES PATENT OFFICE Auguste J. Paris, Jr., Bradford, Pa.

Application October 25,

8 Claims.

This invention relates to a method of treating hydrocarbon oils, and particularly unsaturated hydrocarbon oils or such oils which contain unsaturates, such as motor fuels and lubricating oils.

It is well known that in lubrication of machinery moving at high speeds, a substantial vamount of frictional heat is generated; likewise, in the operation of many engines, such as 10 internal combustion engines and the like, the

parts tobe lubricated are subjected to heat transmitted from the engine cylinders as well as to the heat generated by the friction of the moving parts. Such heat, regardless of how generated,

is'transmitted to the lubricating oil and frequently raises its temperature to a degree sufficient under the existing conditions to crack or decompose a portion of the oil with the resulting deposition of'hard residual carbon If the lubricating system is not a circulatory one, the residual carbon gradually fills the oil space between the moving parts and thereby reduces 1 the space normally available for the on between the moving parts and increases friction; Continued deposition of such carbon eventually requires that the machinery be dismantled and the bearing be cleaned, or else results'in a burned out hearing. In those cases where the lubricating oil is maintained in a circulatory system, as in an internal combustion engine, the circulating undecomposed oil takes up the carbon and it gradually becomes dispersed in fine particles throughout the circulating body'of oil and renders the oil less suitable for lubricating purposes. The disadvantages of the deposition of hard carbon in lubricating oils are appreciated by lubricating engineers and it is now common practice to insert oil filters in circulatory lubricating systems for separating carbon so deposited in 40 the oil, and any other solid bodieswhich may find their way into the circulating body of lubricating oil. Such filters even when new and clean seldom separate all of the finely dispersed carbon particles and their efficiency is well known to gradually decrease with use. At best, the filtration of the oil merely tends to eliminate the presence of the hard carbon particles after they have been formed. 1

Contrary to the present practice of filtering the lubricating oil to remove the'dispersed particles of hard residual carbon, I have found that hydrocarbon oils may be treated so that the 5 carbon resulting from the cracking or decom position of the oil, instead of being hard and causing a deterioration of the lubricating prop- 1934, Serial No. 750,007

erties of the body of oil, will be of a graphitic character in that it is soft and of a very fine texture, and will actually improve the lubricating properties of the body of oil.

The extent to which lubricating oils when treated as contemplated by this invention are improved is shown by the fact that oils so treated have been used as the lubricant for internal combustion engines in automobiles, and after driving an automobile for over six thousand miles without changing the oil, the oil in the crankcase on analysis was found to have maintained its body and to have lubricating properties superior to the oil originally introduced into the crankcase of the engine. When oil so treated is used as the lubricant for internal combustion engines, for example, under most conditions it is not necessary that the oil be changed at short intervals, and it is only necessary that oil;

be added from time to time to replenish that which is gradually used up during the operation of the engine.

Likewise, it is known that hydrocarbon oils which are used as fuels, and particularly as fuels for motor vehicles, on decomposition form a hard and abrasive carbon and that such carbon, when formed in the cylinders of an internal combustion engine, interferes with the normal operation of the engine.

When hydrocarbon oils such as cracked gasoline, and those capable of use for lubrication, are treated as hereinafter set forth and are subsequently used as a motor fuel, or as the lubricant for an internal combustion engine, the carbon deposited in the combustion chambers of the engine as a result of the decomposition of the oil is of a graphitic nature and does not strongly adhere to the cylinder walls and may readily be wiped oil. The presence of such carbon in the combustion chamber does not interfere with the normal operation of the engine, but actually improves the engine operation, as it prevents knocking of the engine and otherwise gives smoother engine performance.

In accordance with the present invention, hydrocarbon oils, such as cracked gasoline and those ordinarily termed lubricating oils, as well as lighter oils such as those now classified as heavy distillate fuel oils, gas oils or spindle oils, are treated in such manner that they are caused to absorb or entrain or unite with substantial amounts of a nitrogen-containing, non-oxidizing gas so that upon decomposition, the oil will yield as one of the decomposition products the desired form of carbon. Products of combustion When absorbed or entrained by hydrocarbon oils have been found. particularly efficacious in producing the soft carbon of the type above referred to, and while products of combustion from various sources may be used as the nitrogen-containing, non-oxidizing gas, it frequently is very desirable and convenient to use the products of combustion of an internal combustion engine.

The manner of treating thehydrocarbon oils which I have found to be most effective in causing them to absorb or entrain nitrogen-containing, non-oxidizing gases is to subject such oils to pressure in the presence of the gas. Oils so treated have been found to retain gases so absorbed or entrained for long periods, and even when heated to temperatures well above 500 F.

Various ways and forms of apparatus may be used for causing the oils to be subjected to pressure in the presence of the nitrogen-containing, non-oxidizing gas. A form of apparatus which I have found to be particularly desirable from the standpoint of effectiveness and simplicity is that shown in the accompanying drawing which more or less diagrammatically represents a compressor and associated parts in which the oil is treated. However, it is to be understood that the method as hereinafter claimed is not to be considered as in any way limited to being carried out in any particular apparatus except as may be particularly indicated in those claims. a

In the accompanying drawing the numeral I represents a compressor cylinder having a piston 2 operated by a piston rod 9 connected to a crank shaft 4 which may be driven in any suitable manner. An hydrocarbon-oil conduit 5 and a nitrogen-containing, non-oxidizing gas conduit 6 communicate with'the interior of the compressor cylinder adjacent the lower end thereof. These conduits are provided with suitable valves l and 8, respectively, whereby the amount of hydrocarbon oil and/or the amount of nitrogen-containing, non-oxidizing gas introduced into the compression cylinder may be regulated. An outlet conduit 9 for the treated oil and any nitrogen-con taining, non-oxidizing gas which is not absorbed or entrained by or united with the oil leads from the upper end of the compressor cylinder. The discharge of the treated oil and gases through the conduit 9 is controlled by a valve I9 operated in synchronism with the piston 2 or any suitable means, such as those generally indicated at I I.

The order in which the oil and gases are introduced into the zone of compression is not material. As shown, the hydrocarbon oil inlet is located at a level lower than that at which the inlet for the nitrogen-containing, non-oxidizing gases is located so that as the piston moves forward on the compression stroke, it will first close the inlet for the hydrocarbon oil and thereafter close the inlet for the nitrogen-containing, nonoxidizing gases.

As it may be desirable to cool the compressed mixture of oil andgases, the discharge pipe 9 leads to a water-cooled condenser I2 having a water inlet I3 and. a water outlet It. Any oil which may be vaporized by the heat of compression is condensed in the condenser I2. treated oil, together with any condensate and any of the nitrogen-containing, non-oxidizing gaseswhich were not absorbed by the liquid hydrocarbons during the compression pass from the water condenser I2 to a trap i5 from which the hydrocarbon oils containing the absorbed or entrained nitrogen-containing, non-oxidizing gases may be drained through a pipe I6 having a con- The trol valve I1 therein. The unabsorbed gases pass from the top of the trap I 5 through an outlet pipe I8 containing a back pressure valve I9 which is adapted to maintain the desired pressure in the system.

The trap I5 is also provided with a pressure gauge 2|] which will indicate the pressure in the system and a liquid gauge 2! which will indicate the amount of treated liquid oil in the trap I5.

It will be understood that upon a downward movement of the piston 2 the inlet from the nitrogen-containing, non-oxidizing gas conduit 6 will be uncovered and a regulated amount of the gas will be introduced into the compression chamber. Upon a further downward movement of the piston 2, the inlet from the hydrocarbon oil conduit 5 will be uncovered by the piston 2 and a regulated amount of the oil will be introduced into the chamber I. As the piston moves forward on the compression stroke, the hydrocarbon oil will be subjected to pressure in the presence of the nitrogen-containing, non-oxidizing gas and will be caused to absorb or entrain or unite with a portion of the gas. Shortly prior to the end of the forward movement of the piston 2 the outlet valve I I] will be opened and the treated oil and unabsorbed gases will pass, upon further movement of the piston, through the discharge pipe 9 to the condenser I2. The treated oil together with any condensate will pas to the trap I5 from which it will be recovered.

In order that the temperatures of the hydrocarbon oil and the nitrogen-contaim'ng, nonoxidizing gas entering the compressor cylinder I may be regulated and maintained at the desired temperature, heat exchangers 22 and 23 are preferably interposed in the hydrocarbon oil conduit 5 and the nitrogen-containing, non-oxidizing gas conduit 6. Suitable means may be provided to cool the compressor I in order to dissipate the heat of compression. Suitable means may also be provided for maintaining the hydrocarbon oil and the nitrogen-containing, non-oxidizing gas under any desired pressure before their introduction into the cylinder.

The temperature of the hydrocarbon oils and the nitrogen-containing, non-oxidizing gas at the time of compression may vary over a substantial range, but thetemperatures prior to introduction preferably are such that decomposition of the oil does not take place at least prior to compression.

When products of combustion or other gases containing liquid vapors are used as the nitrogencontaining, non-oxidizing gas, they preferably are cooled to a sufficiently low temperature to cause the removal of water and/or other liquid vapors prior to their introduction into the compressor, as'the presence of water or other liquids would have a deleterious effect upon the hydrocarbon oil, particularly when the hydrocarbon oil to be treated is a lubricating oil. Other means,

- such as absorption or the like, may be used to eliminate such liquid vapors if desired.

If the water or other liquids were not removed from the gases prior to the compression of the oil, it would take up or become emulsified with the water or other liquids and such water or other liquids would be found in the oil after compression and a subsequent treatment would be necessary to bring about their removal. However, under certain conditions, the gases may be reheated after the removal of the liquid vapors and prior to their introduction into the compressor.

Likewise, when the nitrogen-containing, nonoxidizing gases contain solid or other impurities they preferably are subjected to a cleaning and/ or purifying treatment to remove any such foreign matter prior to their introduction into the compressor.

The oil as treated above will retain the absorbed or entrained nitrogen-containing, nonoxidizing gases for long periods of time and even if heated to elevated temperatures. Such oils may be handled and sold in the manner in which motor fuels and lubricating oils are now handled and sold and when used under conditions such that cracking or decomposition of the oil or parts thereof take place the carbon resulting from such decomposition will be found to be of a graphitic nature. If the hydrocarbon oil is one used for lubrication the carbon will be readily dispersed throughout the oil and will impart to such oil the improved lubricating properties previously referred to. On the other hand, if the hydrocarbon oil is one used for motor fuels or the like, the carbon formed on. decomposition of the oil will act as a lubricant and will not strongly adhere to the walls of the engine cylinder.

While the oil as treated in accordance with this invention is particularly desirable as a motor fuel or as a lubricant, its use is not limited to those purposes but it may be used in any place where such hydrocarbon oils are now used and as set forth in my copending application, Serial No. 708,311, filed January 25, 1934, of which this application is a continuation in part, oil so treated may be decomposed in the presence of an amount of air or other combustion-supporting gas insufficient to cause complete combustion of the hydrocarbon oil, for the production of carbon suitable for pigment and other purposes. Carbon produced by the thermal decomposition of oil so treated is exceedingly black and therefore particularly desirable as a pigment. However, the 40 production of carbon from oils treated as set forth above forms no part of the present application as the same is claimed in the aforementioned application.

While the present invention is not predicated 45 upon any particular theory, it is my belief that under the conditions of treatment set forth above the nitrogen-containing, non-oxidizing gas is caused to chemically or otherwise combine or unite with the molecules of the hydrocarbon oil,

0 as it has been found that it is the unsaturated hydrocarbons or mixtures of hydrocarbons containing substantial amounts of unsaturates which will take up and retain the greatest amounts of such gases, and will take up and retain such gases 55 without the formation of side products during or subsequent to the pressure treatment. But regardless of the manner in which the nitrogencontaining non-oxidizing gas is retained by the hydrocarbon oil, it is liberated under conditions 60 which will bring about decomposition of the hydrocarbon oil with the result that the decomposition of the oil will take place in the presence of those gases and the soft graphitic carbon above referred to will be one of the products of com- 65 bustion or decomposition.

The invention has been described with particular reference to the treatment of hydrocarbon oils which may be used as motor or similar fuels, or for lubrication. However, the invention is not 70 limited to the treatment of such oils and the same may be practiced with any liquid hydrocarbon which will absorb or entrain or combine with the nitrogen-containing, non-oxidizing gas.

What is claimed is: 1. The method of improving the lubricating temperature conditions such that there is no substantial decomposition of the oil into lighter hydrocarbons, whereby at least a portion of the gas is mixed intimately with and entrained by said oil, and removing the resultant mixture of oil and gas from the zone of compression.

2. The method of improving the characteristics of a hydrocarbon lubricating oil which comprises admitting such oil and a nitrogen-containing, non-oxidizng gas to a zone of compression, compressing said gas and oil under temperature conditions such that there is no destroying of the lubricating value of the oil, whereby at least a portion of the gas is mixed intimately with and entrained by said oil, and removing the resulting mixture of oil and gas from the zone of compression.

3. The method of treating hydrocarbon oil which comprises admitting such oil and a nitrogen-containing, non-oxidizing gas, which substantially is free of water vapor to a zone of compression, compressing said gas and oil under temperature conditions such that there is no substantial decomposition of the oil into lighter hydrocarbons, whereby at least a portion of the gas is mixed intimately with and entrained by said oil, removing the resulting mixture of oil and water-free gas from said zone of compression, and separating the hydrocarbon oil from unabsorbed gas.

4. The method of improving the lubricating characteristics of a hydrocarbon lubricating oil which comprises admitting such oil and gaseous products of combustion which substantially are free of water vapor to a zone of compression, compressing said gas and oil under temperature conditions such that there is no substantial decomposition of the oil into lighter hydrocarbons, whereby at least a portion of the gas is mixed intimately with and entrained by said oil, and removing the resultant mixture of oil and water free gas from the zone of compression.

5. The method of improving the characteristics of a hydrocarbon lubricating oil which comprises admitting such oil and gaseous products of combustion which substantially are free of water vapor to a zone of compression, compressing said gas and oil under temperature conditions such that there is no destroying of the lubricating value of the oil, whereby at least a portion of the .gas is mixed intimately with and entrained by said oil, and removing the resulting mixture of oil and water-free gas from the zone of compression.

6. The method of treating hydrocarbon oil which comprises admitting such oil and gaseous products of combustion which substantially are free of water vapor to a zone of compression, compressing said gas and oil under temperature conditions such that there is no substantial decomposition of the oil into lighter hydrocarbons, whereby at least a portion of the gas is mixed intimately with and entrained by said oil, removing the resulting mixture of oil and water-free gas from said zone of compression, and separating the hydrocarbon oil from unabsorbed gas.

'7. The method of improving the lubricating characteristics of a hydrocarbon oil from the class consisting of lubricating oils, heavy distillate fuel oils and gas oils which comprises admitting such oil and a nitrogen-containing, nonwhich substantially is free of Water vapor to a zone of compression, compressing said gas and oil under temperature conditions such that there; is, no substantial decomposition of the oil into light-v er hydrocarbons, whereby at least a portion or the gas is mixed intimately with and entrained by said oil, removing the resulting mixture of oil and water-free gas from Said 20118 of compression,

and separating the,v hydrocarbon oil from unabsorbed gas.

AIIQUS'IYE J- PARIS! J a. 

